预渗氮对H13钢表面电弧离子镀TiN薄膜性能的影响

采用MIP-800C多功能离子渗镀设备,分别在H13钢表面及经表面渗氮后的H13钢表面渗镀TiN薄膜.对两种状态下渗镀的TiN薄膜层的形貌与相组成进行观察分析,并检测了其显微硬度及膜基结合力.结果表明, 经表面渗氮后的H13钢表面渗镀的TiN薄膜较光滑致密,少有大颗粒出现;其显微硬度比未经表面渗氮渗镀的略高(由1831 HV0.025提高到2107HV0.025), 而膜基结合力(78 N)约为后者(44 N)的两倍.预先对H13钢进行表面渗氮能显著提高渗镀的TiN薄膜与基体的结合力及其力学性能.     

ZL109铝合金表面多弧离子镀TiN薄膜的制备及性能

利用正交设计试验探讨了基体温度、偏压、溅射时间、沉积时间对ZL109表面沉积TiN涂层时,对薄膜显微硬度和膜/基结合力的影响.结果表明,在ZL109表面多弧离子镀制备TiN薄膜的最佳工艺为:基体温度260 ℃、偏压200 V、沉积时间30 min、溅射时间8 min、Ti靶电流80 A、炉内总压1 Pa(Ar和N_2流量比为1∶2).在此工艺下制备的TiN薄膜显微硬度达到1500 HV0.05,膜/基结合力达到36 N,膜厚约2～3 μm.     

Ti-Si-N纳米复相薄膜及Si含量对脉冲直流PCVD镀膜质量的影响

用工业型脉冲直流等离子体增强化学气相沉积(PCVD)设备，在高速钢(W18Cr4V)表面沉积Ti-Si-N三元薄膜，研究了不同N2流量对薄膜组织及性能的影响，结果表明：随N2流量增大，膜层沉积速率及膜层中Si含量减少，薄膜组织趋于致密，膜层颗粒尺寸明显减小，划痕法临界载荷和显微硬度显著增加，硬度最高可达50GPa以上。研究发现，对应N2流量，薄膜相组成发生变化，依次存在有TiN／a-Si3N4／Si，TiN／a—Si3N4／TiSi2／Si，TiN／a—Si3N4／TiSi2三种相组成形式，分析认为，低N2或高Si效果不佳的原因在于直流PCVD是以工件为阴极，膜层中过多的Si3N4和Si将严重劣化阴极的电导性，致使膜层疏松，说明脉冲直流PCVD与射频PCVD存在很大的区别。     

调制周期对TiN/Ti多层膜组织结构和结合力的影响

为了阐明调制周期对薄膜微观组织及薄膜与基体结合力的影响,采用反应磁控溅射在Ti6Al4V基板上交替沉积了Ti层及TiN层制备了TiN/Ti多层膜。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、显微硬度仪和划痕仪测量分析了薄膜的晶体结构、微观组织、硬度以及薄膜与基体之间的结合力。研究结果表明:TiN/Ti多层膜中均存在TiN,Ti和Ti2N 3种相。TiN/Ti多层膜均以柱状晶方式生长,在调制周期较大(5层)时,TiN和Ti层的界面清晰;随着调制周期的减小(层数增加),TiN和Ti层的界面逐渐消失。与单层TiN薄膜相比,多层TiN/Ti薄膜的硬度显著提高;但随着薄膜层数的增加,多层TiN/Ti薄膜硬度略微降低。当调制周期为80nm(30层)时,薄膜与基体的结合力明显提高,达到73N。     

Q235钢表面等离子渗镀TiN流量比参数研究

利用双层辉光离子渗金属技术,在Q235钢表面合成TiN渗镀层,从渗镀层厚度、相结构、表面形貌、表面成分、外观和表面显微硬度等方面研究不同的Ar、N2流量比对形成TiN渗镀层的影响.结果表明,Ar、N2流量比对合成TiN渗镀层的厚度基本无影响;随着Ar、N2流量比的降低,TiN渗镀层由(200)转化为(111)择优取向生长;在各流量比下的渗镀层均呈"胞状"形貌,但流量比越低,胞状向外"突起"现象越明显,渗镀层越致密,表面硬度也相对越高;当流量比为8∶ 1时,TiN渗镀层表面Ti、N原子个数比最接近1∶ 1; TiN渗镀层表面颜色随着Ar、N2流量比的变化而不同,其实质是渗镀层中ε-Ti2N相、α-Fe相和ε-TiN相的含量不同,随着N2比例的提高,TiN渗镀层颜色由浅黄-黄色-金黄-深黄色变化,金黄色的渗镀层表面硬度最高;最佳Ar、N2流量比参数为8∶ 1,此时TiN渗镀层表面显微硬度平均值最高,达到了3120 HV0.05.     

非对称双极脉冲磁控溅射制备Ti-Co-La-N纳米薄膜性能

利用非对称双极脉冲磁控溅射制备了不用Co-La掺杂量的Ti-Co-La-N纳米复合薄膜.分别用扫描电子显微镜、X射线衍射、纳米压痕仪、划痕仪以及摩擦磨损仪研究了薄膜的表面形貌、结合力、显微硬度和摩擦学性能.结果表明:复合薄膜主要有TiN相、Co2N相和LaN相组成;复合膜的纤维硬度达到14.61 GPa,低于TiN的显微硬度;复合薄膜的显微硬度和结合力都随着Co-La掺杂量的增加而降低;在高速钢基体上复合薄膜的摩擦系数达到了0.6.     

Ar/N2流量比对辉光等离子渗镀TiN的影响

利用双层辉光等离子渗金属技术,在碳钢表面合成TiN,研究不同的Ar/N2流量比对合成的TiN的影响,获得Ar/N2流量比与TiN表面硬度、表面颜色及TiN成分含量之间的关系,以及Ar/N2流量比对TiN相结构的影响结果:当Ar/N2流量比较大时,以{100}择优取向生长;随着Ar/N2的降低,TiN薄膜由{100}择优取向生长向{111}择优取向生长过渡;TiN薄膜中并不一定是单一的TiN相,还有其他如Ti2N相的存在,造成TiN薄膜硬度的降低.     

脉冲偏压磁过滤电弧离子镀TiN薄膜的组织结构及耐磨性研究

利用脉冲偏压磁过滤电弧离子镀在高速钢(M2)基底上沉积了厚约2.5μm的TiN薄膜;分别采用FESEM、GDOES、XRD和划痕试验法观察薄膜表面和断面形貌、测试薄膜成分及相结构,分析膜基结合强度,通过显微硬度计和球盘摩擦磨损试验机对比考察TiN薄膜和M2高速钢基体的硬度和耐磨性。结果表明,TiN薄膜表面光滑致密,呈现致密柱状晶结构和明显的(111)择优取向,膜基结合强度大于60 N,薄膜硬度约为26 GPa;脉冲偏压磁过滤电弧离子镀制备的TiN薄膜表现出很好的减摩和耐磨性能。     

硬质合金表面多弧离子镀(Ti,Al,Zr,Cr)N多元氮化物膜

采用Ti-Al-Zr合金靶和Cr靶,用多弧离子镀技术在WC-8%Co硬质合金基体上沉积(Ti,Al,Zr,Cr)N多元氮化物膜。分析了薄膜的成分、形貌、粗糙度和结构,研究了薄膜的显微硬度、膜/基结合力和抗高温氧化性能。结果表明,获得的多元氮化物膜仍是B1-NaCl型TiN面心立方结构;适当控制偏压条件可以改善薄膜的表面形貌;在不同的偏压条件下,(Al+Zr+Cr)/(Ti+Al+Zr+Cr)的成分比为0.41～0.43,当其比值趋于0.4时,薄膜的显微硬度和膜/基结合力达到最大值3600HV0.01和200N;同时薄膜的抗高温氧化性能提高,最高温度可达700℃左右。     

离子氮化40Cr与TiN和TiAlN复合处理的组织与性能

对40Cr分别进行TiN和TiAlN涂层复合处理,对比研究了二者的组织与性能。结果表明,两种致密、均匀的涂层沉积在离子氮化表面能够降低表面粗糙度。TiN涂层的物相主要是TiN与Ti_2N,表面硬度达到2700 HV0.2,结合力15 N;Ti lN涂层则主要由Fe_4N、(Ti,Al)N和TiN等相组成,表面硬度达到3000 HV0.2,结合力为17 N;氮化与涂层的复合处理相比于氮化处理能够获得更高的硬度。TiN涂层硬度较低、脆性较大,在相同的加载条件下,磨损更为严重,磨痕边缘涂层变形与剥落更加明显;TiAlN涂层磨痕宽度均匀,磨损量低,耐磨性最高。     

基体温度对磁控溅射TiN薄膜电化学性能的影响

采用直流反应磁控溅射方法在AISI 304不锈钢和Si(100)表面沉积了TiN薄膜,利用场发射扫描电镜、X射线衍射仪和电化学技术研究了基体温度对TiN薄膜结构与电化学性能的影响。结果表明:TiN薄膜为柱状结构,表面平整、致密,但基体温度高于300℃时膜表面存在微裂纹。薄膜为面心立方结构δ-TiN并存在择优取向,室温和150℃时的薄膜择优取向为(111)晶面,300℃和450℃时为(200)晶面;基体为室温时薄膜厚度为0.63μm,温度提高到150℃后膜厚增加到1μm左右,但继续升温对膜厚影响并不明显。薄膜在NaCl溶液中的腐蚀为点蚀,基体温度为150℃时的TiN薄膜具有最高的开路电位和点蚀电位以及最低的腐蚀速率,因此具有最佳的耐蚀性。     

高速钢的离子镀—渗镀复合处理

对离子镀-渗镀复合处理工艺制备多元膜工艺进行了研究。结果表明,离子镀TiN-高温渗Cr复合工艺可在高速钢基形成含Cr的氮化物多元膜,膜层由（TiCr)N、β-（CrTi）2N和Ti相组成,具有比TiN高的硬度,在膜/基界面区形成由Cr7C3和M6C组成的富Cr过渡层,具有改善膜/基附着力的作用。     

Composite TiN–Ni thin films deposited by reactive magnetron sputter ion-plating

Composite TiN–Ni thin films were deposited by direct-current (DC) magnetron sputter ion-plating from an alloy Ti–48 at% Ni target in a mixture of argon and nitrogen gases at a total pressure of 0.1 Pa onto glass and stainless steel substrates heated to temperatures higher than 250 °C. The films deposited at the nitrogen flow Q_N2≥6.4 sccm consisted of a mixture of δ-TiN and fcc nickel phases. The effects of negative substrate bias and substrate temperature on the crystal structure of the films were studied. The substrate bias of −200 V resulted in improved crystallization of films and a smaller difference in size between the TiN and nickel grains, as compared with films deposited onto substrates at floating potential. It was possible to vary the crystal grain size of both phases by varying the substrate temperature in the range 270–430 °C. The maximum hardness measured in the films was 10.5 GPa. It is expected that the hardness can be increased by decreasing the content of nickel.     

Study of adhesion of TiN grown on a polymer substrate

TiN films were deposited on polycarbonate substrates by cathodic vacuum arc using the plasma immersion ion implantation and deposition (PIII&D) method. The biaxial intrinsic stress in the film deposited using PIII&D with 3 kV applied bias was 0.3 GPa — much lower than that found in films deposited without the application of high-voltage pulsed bias. It was found that the dominant mechanism for generating stress in the TiN film was thermal stress arising from the large difference between the thermal expansion coefficient of TiN and that of the polymer. Tensile testing was used to ascertain film adhesion and a model was used to estimate the adhesion between the film and the substrate. It was found that PIII&D strongly reduced the stress in the TiN film and increased the adhesion to the polycarbonate. The ultimate shear strength of adhesion is of the same order of magnitude as that of TiN on stainless steel.     

The effect of deposition conditions on the properties of TiN thin films prepared by filtered cathodic vacuum-arc technique

Thin TiN films were deposited at ambient temperature on silicon substrates using the filtered cathodic vacuum-arc technique. The nitrogen flow rate, deposition rate and substrate bias were varied systematically to investigate their effect on the mechanical and structural properties of the films. It was found that an increase in the nitrogen flow rate results in an increased hardness, surface roughness and grain size. The increased ion bombardment due to the higher amount of nitrogen ions makes film nucleation favourable on the denser (111) orientation. An increase in deposition rate results in an increase of stress, hardness and surface roughness. This is due to the increase in the momentum transfer resulting in film densification. Increasing the negative substrate bias decreases both the film stress and the hardness, which can be attributed to ion-induced stress-relief behaviour at higher momentum-energy transfer. The results demonstrate the dominant influence of ion-energy flux on the properties of the films.     

Effect of Axial Magnetic Field on the Microstructure and Mechanical Properties of CrN Films Deposited by Arc Ion Plating

CrN films were deposited on the high-speed-steel substrates by arc ion plating. The effect of an axial magnetic field on the microstructure and mechanical properties was investigated. The chemical composition, microstructure, surface morphology, surface roughness, hardness and film/substrate adhesion of the film were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope(SEM), surface morphology analyzer, Vickers microhardness test and scratch test. The results showed that the magnetic field puts much effect on the microstructure,chemical composition, hardness and film/substrate adhesion of the Cr N films. The N content increases and Cr content decreases when the magnetic flux density increases from 0 to 30 m T. All of the Cr N films were found to be substoichiometric. With an increase in the magnetic flux density, the film structures change in such way: Cr_2N →Cr_(2-N)+CrN→CrN+Cr_2N→CrN.The SEM results showed that the number of macroparticles(MPs) on the film surface is significantly reduced when the magnetic flux density increases to 10 mT or higher. The surface roughness decreases with the magnetic field, which is attributed to the fewer MPs and sputtered craters on the film surface. The hardness value increases from 2074 HV_(0.025) at 0 mT(without magnetic field) and reaches a maximum value of 2509 HV_(0.025) at 10 m T.The further increase in the magnetic flux density leads to a decrease in the film hardness. The critical load of film/substrate adhesion shows a monotonous increase with the increase in magnetic flux density.     

硬质合金刀具ZrC涂层的沉积

采用原位卤化反应直接形成的ZrCl4气体作为Zr源,在硬质合金刀具上沉积CVD-ZrC涂层。用SEM,XRD分析检测了合金刀具基底不同表面上沉积生长ZrC涂层的厚度均匀性、沉积速率、形貌组织、织构取向;通过理论计算与工艺实际的涂层沉积转化率对比,定量表征了该沉积体系工艺参数下ZrC涂层的沉积转化率。结果显示,CVD涂层炉内不同位置合金刀片表面沉积的ZrC涂层均匀;由于工艺温度限制,涂层沉积速率较低;ZrCl4转化为ZrC涂层的工艺实际转化率约11%,在理论最大转化率14%范围内;相同温度下随着沉积压力升高,涂层的沉积转化率缓慢降低到10%并趋于稳定;直接在合金基底沉积形成的ZrC涂层为细小的颗粒状形貌,而在合金基底TiN涂层表面上沉积生长的ZrC具有典型的片状组织形貌;对应的涂层生长织构取向从(311)到(111)转变。     

Effects of titanium-implanted pre-treatments on the residual stress of TiN coatings on high-speed steel substrates

This investigation examined how titanium ion implantation pre-treatment affects the residual stress of TiN coatings on M2 high-speed steel. Ions were implanted by metal plasma ion implantation. The adhesion strength of the TiN coatings was enhanced by pre-treatment that implanted Ti into the M2 tool steel substrate. The implanted substrate functioned as a buffer layer between the deposited TiN and the tool steel substrate, resulting in variations of the residual stress. The residual stress determined by glancing-angle XRD demonstrates that the deposited TiN films on ion-implanted substrates exhibited reduced compressive stress, from − 3.95 to − 2.41 GPa, which corresponded to a decrease in the grain size of the TiN films. The texture of the TiN film was clearly transformed from the preferred orientation of (220) to (111), subsequently enhancing wear resistance against a tungsten ball.     

Room-temperature growth of high-purity titanium nitride by laser ablation of titanium in a nitrogen atmosphere

Thin films of titanium nitride (TiN) were deposited on glass substrates by KrF excimer laser ablation of titanium over a very broad nitrogen pressure range with different target–substrate distances at room temperature. The as-deposited TiN thin films were analyzed by X-ray diffraction and transmission electron microscopy. It was found that the as-deposited thin films are normally a mixture of TiN and metallic titanium, and the TiN-to-Ti ratio of the as-deposited thin film depends on both the nitrogen pressure and the target–substrate distance. High-purity TiN thin films can be obtained only in a very narrow deposition parameter range. A compound parameter (the product of the nitrogen pressure and the target–substrate distance) is proposed to optimize the deposition of high-purity TiN thin films, and the possible mechanism is also discussed. It was also revealed that the as-deposited TiN thin films are polycrystalline with an average grain size of about 20 nm.     

多弧离子镀制备TiN涂层的高温抗氧化性能研究

在201不锈钢上进行多弧离子镀沉积TiN涂层,研究了TiN涂层在400～800℃间的高温氧化性能。对涂层氧化后的表面形貌、表面成分等进行了研究。用热重(TG)法和差示扫描量热(DSC)法分析粉末试样的加热氧化情况。结果表明:氧化温度较高时,增重量大且氧化严重,随着氧化温度的升高,表面氧元素含量上升,氮元素含量下降;经过600℃氧化,TiN膜层开始出现局部氧化皮。热分析结果表明:TiN粉末在450℃开始发生增重,氧化总增重量为26.63%。起始氧化温度为623.7℃,放热焓为-2112μVs/mg。